EP1562694B1 - Membrane pour filtration tangentielle et son procede de fabrication - Google Patents

Membrane pour filtration tangentielle et son procede de fabrication Download PDF

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Publication number
EP1562694B1
EP1562694B1 EP03778408A EP03778408A EP1562694B1 EP 1562694 B1 EP1562694 B1 EP 1562694B1 EP 03778408 A EP03778408 A EP 03778408A EP 03778408 A EP03778408 A EP 03778408A EP 1562694 B1 EP1562694 B1 EP 1562694B1
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Prior art keywords
support
fluid
membrane
treated
flow
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German (de)
English (en)
French (fr)
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EP1562694A1 (fr
Inventor
Philippe Lescoche
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Technologies Avancees et Membranes Industrielles SA
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Technologies Avancees et Membranes Industrielles SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/061—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B01D63/063—Tubular membrane modules with membranes on a surface of a support tube on the inner surface thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material

Definitions

  • the present invention relates to the technical field of tangential separation using separation elements generally called membranes made from inorganic materials and consisting of a porous support delimiting at least one circulation channel for a fluid medium, on the surface of which is deposited at least one separating layer whose nature and morphology are adapted to ensure the separation of the molecules or particles contained in the fluid medium to be treated.
  • separation elements generally called membranes made from inorganic materials and consisting of a porous support delimiting at least one circulation channel for a fluid medium, on the surface of which is deposited at least one separating layer whose nature and morphology are adapted to ensure the separation of the molecules or particles contained in the fluid medium to be treated.
  • the object of the invention is, more specifically, the production of a porous support.
  • the object of the invention finds a particularly advantageous application in the field of nanofiltration, ultrafiltration, microfiltration, filtration or reverse osmosis.
  • a membrane is defined by the combination of a porous support of inorganic material, such as ceramic, and of one or more inorganic separating layers deposited on the surface of each circulation channel and linked to each other and to the support, by sintering.
  • These membranes can adopt different geometries.
  • the role of the layers is to ensure the separation of molecular or particulate species, while the role of the support is to allow, by its mechanical strength, the realization of thin layers.
  • the rigid porous support is of elongated shape having a polygonal or circular cross section.
  • the porous support is arranged to include at least one and preferably a series of channels parallel to each other and to the longitudinal axis of the porous support, each having a cylindrical shape.
  • the channels communicate, on one side, with an inlet chamber for the fluid medium to be treated and, on the other side, with an outlet chamber.
  • the surface of the channels is covered with at least one separating layer ensuring the separation of the molecules or particles contained in the fluid medium flowing inside the channels, in a given direction, from one end of the so-called inlet channels to the other so-called output end.
  • Such a membrane carries out, by sieve effect, a separation of the molecular or particulate species of the product to be treated, insofar as all the particles or molecules greater than the diameter of the pores of the membrane are arrested.
  • the fluid is transferred through the separator layer, and then the fluid spreads through the permeability of the support to the outer surface of the porous support.
  • the portion of the fluid to be treated having passed through the separation layer and the porous support is called permeate and is recovered by a collection chamber surrounding the membrane.
  • the porous support is in the form of a block in which is arranged at least one, and in general a series of superimposed channels each having a generally rectangular polygonal cross section.
  • the surface of the channels is covered with at least one separating layer.
  • the fluid to be treated circulates at high speed over the surface of the channels in order to generate a shear stress that redisperses the materials deposited on this surface. It thus appears a friction of the fluid on the surface of the channels leading to the existence of a loss of charge which varies linearly depending on the length of the channels.
  • This pressure drop depends on dimensional parameters such as the length of the membrane, its hydraulic diameter and experimental parameters, such as the circulation velocity, the viscosity and the density of the fluid to be treated.
  • the US Patent 4,105,547 describes a tangential filtration apparatus implementing a system for compensation of the longitudinal pressure drop.
  • a system for compensation of the longitudinal pressure drop consists in ensuring the circulation of the permeate tangentially outside the membrane, in the same direction as the fluid to be treated circulating tangentially in the channels.
  • the pressure drop of the permeate flow is identical to that of the fluid to be treated. There is therefore a compensation between the two pressure drops, so that the pressure is the same at all points along the channels.
  • EP 0 333 753 is an improvement of this system. It consists in arranging balls in the permeate compartment in order to obtain identical pressure losses to that of the liquid to be treated with a very low flow rate of circulation.
  • patent EP 0 870 534 B1 proposes a macroporous support whose external porosity is modified, so as to reveal a porosity gradient all along the support.
  • This porosity gradient shows a gradient of permeability. Due to the pressure variation, the permeate flow through the membrane becomes constant. If such a solution makes it possible to modify only the support, this technique has the drawback of reducing the external porosity of the support thus facilitating the accumulation of the molecules or particles which have passed through the separating layer and which, statistically, can be stopped by the part of the support with reduced porosity.
  • the diameter of the pores along a cross section of such a support increases and then decreases at its periphery, so that there is a risk of accumulation for the molecules or particles. Such an accumulation is likely to lead to the destruction of the support.
  • the reduction of the porosity is carried out solely on the outer ring of the porous support.
  • the porosity of the support in its internal portion adjacent to the separation layer, is not reduced.
  • the pressure inside the channels decreases in the direction of flow of the fluid to be treated.
  • the permeate after having passed through the separating layer, spreads in the internal porosity and flows outward looking for an area requiring less energy. The permeate then flows mainly through the part of the most porous support. In these circumstances, the Porosity gradient thus produced leads to the appearance of heterogeneous permeate flow rates along the length of the membrane.
  • the patent application EP 1 074 291 proposes a solution for obtaining a uniform permeate flow all along the membrane.
  • This solution consists in depositing on the macroporous support a separation layer having a gradient of thickness decreasing in the direction of flow of the fluid to be treated.
  • the support makes it possible to ensure the mechanical strength without participating in the hydraulic resistance of the membrane, while the separation layer defines the permeability without participating in the mechanical strength.
  • the object of the invention is therefore to provide an alternative solution to overcome the disadvantages mentioned above by providing a tangential filtration membrane adapted to obtain a permeate flow more homogeneous along the membrane and not having a fragile zone where accumulate species of the fluid to be treated, retained by the membrane.
  • the solution proposed by the invention consists in modifying the porous support on its part adjacent to the separation layer to make it participate in the permeability of the membrane.
  • the membrane for tangential filtration of a fluid to be treated comprises a porous support delimiting at least one circulation channel for the fluid to be treated circulating in a given direction between an inlet and an outlet, the surface internal of the porous support delimiting the channel being covered by at least one separation layer for the fluid to be treated, a fraction called permeate passing through the separation layer and the porous support.
  • the carrier has a variable partial seal extending from the inner surface of the carrier on which the separation layer is deposited.
  • Cdit clogging creates, on a wafer of the support of given constant thickness extending from the internal surface of the support, a mean porosity gradient, according to the direction of flow of the fluid to be treated, the minimum average porosity being located at entrance and the maximum average porosity at the exit.
  • the object of the invention is also to provide a method of manufacturing a membrane for tangential filtration of a fluid.
  • a method of manufacturing a membrane for tangential filtration of a fluid comprises a step of modifying the porous support by penetration, from the inner surface of the porous support delimiting the channel of circulation, inorganic particles of average diameter less than the average diameter dp of the pores of the support, so as to obtain on a given constant thickness wafer extending from the inner surface of the support, a mean porosity gradient, according to the flow direction of the fluid to be treated, the minimum mean porosity being located at the inlet and the maximum mean porosity at the outlet.
  • the Fig. 1 is a cross-sectional view of an exemplary embodiment of a membrane according to the invention.
  • the Fig. 2 is a longitudinal sectional view of a membrane taken substantially along the lines II-II of the Fig. 1 .
  • the Fig. 3 is a view similar to the Fig. 2 illustrating another variant of a membrane according to the invention.
  • Fig. 4 to 16 are tables giving the experimental measurements, respectively, for a membrane of the prior art and for membranes according to the invention.
  • Porosity denotes the pore volume of the support relative to the total apparent volume of the support. Porosity is measured, for example, by mercury porometry. It is a device that sends mercury under pressure into a porous sample. This apparatus gives the distribution of the pore diameters but also the porosity of the porous body.
  • the density of flow per unit of pressure and the permeability of a porous support reflect the ease with which a fluid medium passes through said support.
  • the density of flux refers to the quantity in m 3 of permeate passing through the surface unit (in m 2 ) of support per unit of time (in s).
  • the flux density per unit of pressure is therefore measured in m 3 / m 2 / s / Pa ⁇ 10 -12 .
  • the permeability in the sense of the invention, corresponds to the flow density per unit of pressure reduced to the thickness and is expressed in m 3 / m 2 / s / m / Pa x 10 -12 .
  • the filtration membrane 1 is adapted to ensure the separation or filtration of molecules or particles contained in a fluid medium, preferably liquid, of various natures, comprising a solid phase or not.
  • the geometry of the filtration membrane 1 is of the tubular type.
  • the filtration membrane 1 comprises an inorganic rigid porous support 2 , made of a material whose transfer resistance is suitable for the separation to be carried out.
  • the porous support 2 is made from inorganic materials, such as metal oxides. , carbon or metals.
  • the porous support 2 is made in an elongated shape extending along a longitudinal central axis A.
  • the porous support 2 has a polygonal transverse cross-section or, as in the example shown in FIGS. fig.1 and 2 , a circular cross section.
  • the porous support 2 thus has an outer cylindrical surface 2 1 of circular section.
  • the porous support 2 is arranged to include at least one and, for example illustrated, a channel 3 made parallel to the axis A of the support.
  • the channel has a cross section that is transverse to the axis A of the support, of cylindrical shape.
  • the channel 3 has an internal surface 4 covered by at least one separation layer 5 , intended to be in contact with the fluid medium to be treated, circulating inside the channel 3 in a direction of circulation represented by the arrows f allowing determining an input 6 and an output 7 for such a membrane operating in tangential mode.
  • the nature of the separating layer or layers 5 is chosen as a function of the separation or filtration power to be obtained and forms, with the porous support 2 , an intimate bond so that the pressure originating from the liquid medium is transmitted to the porous support 2 .
  • This or these layers may be deposited from, for example, suspensions containing at least one metal oxide conventionally used in the production of the elements of mineral filtration. This or these layers are subjected after drying to a sintering operation which allows them to be consolidated and bonded together and to the porous support 2 . Part of the fluid medium passes through the separating layer 5 and the porous support 2 , so that this treated part of the fluid, called permeate, flows through the outer surface 2 1 of the porous support.
  • the part of the support 2 adjacent to the separation layer 5 is modified relative to the rest of the support.
  • the support 2 has a variable partial sealing which extends along the support, from the inner surface 4 of the support 2 on which the separation layer 5 is deposited.
  • This clogging is said to be “partial” because the support is not completely clogged since it allows the permeate to pass.
  • This clogging is said to be “variable” because it varies as one moves along the support 2 and thus creates, on a wafer 8 of constant thickness given e extending from the inner surface 4 of the support 2 , a average porosity gradient, according to the direction of flow f of the fluid to be treated.
  • the portion of the most clogged slice 8 with the lowest average porosity is located at the inlet 6 of the membrane, while the least clogged portion having the highest average porosity is located at the outlet 7 of the membrane. . Therefore, the flow density per unit pressure increases along the support 2 , between the inlet 6 and the outlet 7. Also, the permeate flow through the separation layer 5 and the porous support 2 is constant along the membrane, insofar as the average porosity gradient and therefore the flow density gradient per unit of pressure vary inversely proportional to the pressure exerted by the fluid medium to be separated. Indeed, the pressure of the fluid to be treated decreases in the direction of flow f of the fluid, namely from the inlet 6 to the outlet 7 of the membrane. The flux density gradient per unit pressure of the layer is therefore chosen so as to obtain a constant permeate flow over the entire length of the membrane.
  • the invention has another interest. Inside the support described in EP patent 0 870 534 B1 , the average pore diameter increases and then decreases as one moves transversely to the flow direction of the fluid, from the separation layer to the outer surface of the support, thus favoring accumulation zones. On the contrary, according to the invention, the average porosity of the support increases within the support 2, and in particular within the slice 8, when moving, transversely to the flow direction f of the fluid to be treated, the inner surface 4 of the support 2 to the outer surface 2 1 of the latter .
  • the average porosity gradient is achieved by penetration from the inner surface 4 of the support 2 of particles of average diameter smaller than the average diameter of the pores of the support 2, which makes it possible to obtain a partial clogging of the slice 8 of the support. 2.
  • This wafer 8 extends from the inner surface 4 of the support 2 intended to receive the separation layer 5.
  • the wafer 8 is a volume wafer of constant thickness e. As presented to the fig.2 , the thickness e corresponds to the maximum depth of clogging c, depth determined from the inner surface 4 of the support 2 on which the separation layer 5 is deposited.
  • This clogging c corresponding to the penetration of the particles is carried out on a depth p which depends on the size, ie the diameter of the particles, and the experimental conditions of penetration. In general, the penetration depth p does not exceed a few tens of ⁇ m, a value reached for the finest particles.
  • the existence of a mean porosity gradient on the wafer 8 of constant thickness e means that, if this wafer 8 is divided into a series of equal elementary volumes corresponding to sections extending transversely with respect to the flow direction f of the fluid, the average of the porosities obtained for these elementary volumes increases when moving longitudinally in the direction of flow f of the fluid to be treated.
  • the average porosity can increase substantially continuously along the slice 8 of constant thickness e between the inlet 6 and the outlet 7.
  • the flux density per unit of The pressure also increases substantially continuously between the inlet 6 and the outlet 7.
  • this average porosity gradient can be obtained by penetrating particles from the inner surface 4 of the support to a depth p which decreases substantially continuously, according to the flow direction f of the fluid to be treated.
  • the dimensional ratio between the separation layer 5, the slice 8 and the porous support 2 is not respected: the separation layer 5 and the slice 8 have been represented with larger scales to illustrate the object of the invention.
  • the average porosity can increase, on the wafer 8 of the support 2 of constant thickness e, in steps P i .
  • the flow density per unit of pressure also increases in increments P i between inlet 6 and outlet 7.
  • the length of the sections taken in the direction of circulation f corresponding to the elementary volume for the measurement of the average porosity and the flow density per unit of pressure corresponds to the length of the steps P i .
  • the Fig. 3 illustrates the case where this average porosity gradient is due to a clogging c, corresponding to a penetration of particles according to a depth gradient p.
  • the depth p decreases in P i levels, depending on the direction of flow f of the process fluid between the inlet 6 and the outlet 7. In the example illustrated, there are four levels P 1 to P 4 corresponding to four depths p penetration.
  • the penetration depth p on the bearing P 1 located at the inlet 6 is greater than the penetration depth of the nearest P 2 bearing and so on for the other consecutive bearings.
  • the penetration depth p is constant for each step. It could also be expected that the penetration depth p gradually decreases on each bearing, in the direction of movement f, with a depth jump at the junction between two consecutive bearings.
  • Said bearings are preferably all of length taken in the substantially identical direction of circulation.
  • the examples described above relate to a single-channel membrane comprising a cylindrical channel of substantially ovoid transverse cross-section.
  • the subject of the invention can be implemented on membranes comprising one or more channels of varied and various shapes.
  • the object of the invention can be applied to a membrane having at least one channel 3 of polygonal cross section, arranged in a porous block to form a membrane of the planar type.
  • the porous support 2 comprises a series of superimposed channels 3 each having a rectangular cross section and whose walls are covered with a separating layer 5.
  • the support has a partial clogging as defined above, near each inner surface 4 delimiting a channel 3.
  • the support therefore has a modified porosity, the volume adjacent to the inner surface 4, volume located between a channel 3 and the outer surface 2 1 of the support, or between two channels 3.
  • the object of the invention is also to provide a method for producing a filtration membrane 1 as described above.
  • Such a method comprises a step of modifying the porous support 2 by penetration, from the inner surface 4 of said support, of inorganic particles, with a mean diameter less than average diameter dp of the pores of the support 2. This penetration is performed so as to obtain, on the wafer 8 of constant thickness e, an average porosity gradient, according to the direction of flow of the fluid to be treated, the minimum mean porosity being situated at the entrance and the maximum average porosity at the exit.
  • average diameter less than the average diameter dp of the pores of the support 2 is preferably meant that the average diameter of the inorganic particles is between dp / 100 and dp / 2.
  • the penetration of the particles inside the support 2 is carried out using a deflocculated suspension of such particles.
  • the deflocculation of the suspension is necessary in order to avoid the formation of agglomerates of particles and thus to preserve particles in an individualized form capable of penetrating inside the pores of the support.
  • the suspension advantageously has a low viscosity.
  • Such particles consist of an inorganic material such as metal oxides, the inorganic material constituting the inorganic particles being identical to that constituting the support and / or the separation layer 5.
  • the penetration step is followed by a sintering step which makes it possible to group the particles present in the pores of the solid support 2 causing a magnification and an amalgam of said particles and fixing the clogging of the porous support 2.
  • a sintering step which makes it possible to group the particles present in the pores of the solid support 2 causing a magnification and an amalgam of said particles and fixing the clogging of the porous support 2.
  • the following description is directed to a process for producing a membrane as illustrated in FIG. Fig. 2 .
  • the penetration of particles of the same particle size is carried out inside the pores of the wafer 8 over a depth p measured from the inner surface 4 of the support 2 which decreases in the direction of flow f of the fluid to be treated. .
  • Such a variable penetration depending on the length of the support can be achieved by the method of engobage.
  • This method consists in arranging the porous support 2 vertically and filling the channel 3 with a deflocculated suspension of inorganic particles of average diameter less than average diameter dp of the pores of the support by means of a peristaltic type pump and variable speed.
  • the filling time of the channel is called Tr.
  • the time during which the support is kept filled with the suspension by action on the speed of rotation of the pump is called Ta.
  • the support is then emptied by inversion of the direction of rotation of the pump, the emptying time being called Tv.
  • the three times Tr, Ta, Tv define the contact time Tc between each point of the internal surface 4 of the support 2 and the suspension.
  • the penetration depth p of the particles inside the support depends on the contact time Tc between the porous support 2 and the suspension. Also, it is planned to empty the channels 3 gradually, in order to obtain a contact time Tc between the suspension of particles and the support 2 which increases gradually and substantially continuously between the top of the support corresponding to the outlet 7 and the bottom of the support corresponding to the input 6. It can thus be obtained a penetration depth p which increases from the high end to the low end of the support.
  • Tc contact time
  • Tr , Ta and Tv according to the relation (I)
  • a method may consist of dividing the channel 3 into a series of sections Pi of substantially equal length, for example the number of four P 1 to P 4 in the illustrated example.
  • the surface Channel 3 is then contacted with a deflocculated suspension of particles of average diameter smaller than the average diameter dp of the pores of the support.
  • the penetration depth p is controlled by the concentration parameters of the suspension and the contact time between the suspension and the porous support 2. For the same suspension, the contact time will be decreased by P 4 bearing at P 1 level .
  • Another technique for obtaining a variable clogging c is to perform successive penetrations of inorganic particles having different average diameters, these diameters must always be less than the average pore diameter of the support.
  • two successive penetrations can be made, a first using inorganic particles whose average diameter d 1 is between dp / 100 and dp / 2, then a second made with inorganic particles whose average diameter d 2 d is between 1/100 and 1/2.
  • the manufacture of a porous support having a variable partial clogging extending from the inner surface 4 can be achieved by other methods than those described above.
  • the clogging and therefore the value of the average porosity gradient and flow density per unit of pressure of the slice 8 as a function of the value of the gradient of the pressure of the fluid to be treated flowing in the channel 3 can be obtained.
  • the separation layer 5 may have a decreasing thickness in the direction of flow f of the fluid to be treated, as described in FIG. EP 1 074 291 .
  • the invention then provides to avoid the formation of a deposit on the inner surface 4 of the porous support 2, during the penetration of the inorganic particles inside the support 2.
  • a single-channel support of external diameter 10 mm and internal diameter 6 mm and length 1200 mm is used.
  • This porous support has an average equivalent pore diameter of 5 ⁇ m.
  • a deposit of a titanium oxide slurry is first produced which, after sintering, makes it possible to obtain an equivalent mean diameter for this deposit of 1.5 ⁇ m.
  • the membrane thus produced is cut into 12 sections of length 10 cm, which are measured in permeability to water. This membrane was made for reference, in the absence of clogging.
  • the seals which make it possible to seal the clamp connections are particular in that they comprise a 9.5 mm diameter hole in their centers.
  • the four housings are connected together through their particular joints.
  • the membrane 1178 mm long is disposed inside these four housings, and the assembly is then connected to a pump to obtain flow rates of between 100 and 500 l / h corresponding to respective speeds of 1 and 5 m / s. Under these conditions and through the permeate outlets of each housing, the permeate flow rates are measured for each of the crankcase.
  • the table of the Fig. 6 defines the experimental conditions and gives the obtained filtrate flow values.
  • This example corresponds to the penetration inside the support 2 of a suspension of particles which can also be used to produce a separation layer 5.
  • a suspension of titanium oxide particles having a particle size of 0.5 ⁇ m is prepared. This suspension is deflocculated using a specific agent called COATEX which separates the particles from each other and eliminates any sedimentation. No organic binder is added to obtain a very low viscosity.
  • Single-channel supports of external diameter 10 mm and internal diameter 6 mm and length 1200 mm are used. These porous supports have an average equivalent pore diameter of 5 ⁇ m and are identical to that previously taken as a reference. These supports are then subjected to an engobage operation.
  • the values of Tr, Ta and Tv used are indicated in the table of the Fig. 7 .
  • two supports are modified by penetration of the suspension and then after drying, are calcined at a temperature of the order of 1100 ° C.
  • the supports thus modified are defined by their triplet of values Tr / Ta / Tv, for example 10/10/40.
  • the first modified support of each series is measured in permeability to water through the housing used above. Only one speed (5 m / s) was used for these measurements.
  • the second modified support is cut so as to take samples in the form of thin sections (2 to 3 mm in height) at lengths of 0 mm, 300 mm, 500 mm, 700 mm and 1178 mm. These sections are intended for measuring the penetration inside the support and the thickness of the existing deposit on the inner surface 4 of the support, if such a deposit exists.
  • the table of the Fig. 8 presents the flow values according to the sections.
  • the sections are numbered from 1 to 4, the number 1 corresponding to the bottom of the support during the encapsulation operation.
  • Measurements of the penetration of the particles inside the porosity of the support were made on the sections of small thicknesses taken at the lengths 0 mm, 300 mm, 700 mm and 1178 mm. These sections of low thicknesses were filled with coating resin and then polished to observe in one plane the penetration of particles using a scanning electron microscope.
  • the table of the Fig. 9 shows the particle penetration measurements in the support as well as the thickness of the layers. Examination of this table leads to the conclusion that the particles have actually penetrated inside the porosity of the support from its internal surface 4 and that the depth of penetration is the consequence of the time of contact with the suspension. As indicated above, the contact time at a point of the support depends on the height of this point. The results show that the depth of penetration varies as this contact time and that a penetration depth gradient of flow density per unit of pressure and porosity thus favoring the homogeneity of the permeate flow rates.
  • the particles When the depth of penetration becomes important, the particles can no longer progress within the support. The media can be considered as clogged. But, as the capillary suction is maintained, the particles continue to arrive at the surface of the support and constitute a deposit. This is shown by the thickness values of the layer corresponding to this deposit which are zero when the contact time is low, then become positive and even important for high values of this contact time.
  • the deposit may correspond to the separation layer 5 of the membrane.
  • the inorganic particles used for the penetration step can not be used to make a separation layer 5.
  • the invention avoids the formation of a deposit.
  • the inorganic particles used are titanium oxide particles having a mean particle diameter of 1 ⁇ m. This diameter is obtained after an energetic grinding in a jar containing balls of diameter 5 mm in alumina. These particles are deflocculated via an adjuvant of the COATEX family.
  • the suspension contains no organic binder and the particle concentration is less than 50 g / l. The values of these two parameters are intended to obtain a very low viscosity.
  • the supports are modified by engobage with the aid of this suspension, according to the experimental conditions of the deposit defined in the table of the Fig. 10 .
  • the emptying rate has been significantly increased, in order to achieve a shear stress at the wall of the membrane and thus erode the deposit which could have a tendency to form.
  • the three times 10s, 5s and 3s of emptying respectively correspond to speeds of 0.117 m / s, 0.234 m / s and 0.39 m / s.
  • the table of the Fig. 11 presents the flow rate values measured on these modified supports.
  • the flow values obtained by this method are less homogeneous than with the previous method but they remain much better than those of the reference.
  • the emptying speed improves the homogeneity of flow rates and is therefore an important parameter.
  • the depths of the different penetrations as well as the thicknesses of the deposits, if they exist, were determined according to the previous method.
  • the table of the Fig.12 presents the results obtained. This table shows that the penetration of particles of 1 micron is less important than that of the previous example with particles of 0.5 microns. Whatever the type of modified support, the penetration into the bottom of the latter is always greater than at the top, thus creating a gradient of porosity and thus flow density per unit of pressure favorable to obtain homogeneous flow rates .
  • two powders of particles of different average diameter are used. Two suspensions of these two powders are brought into contact with the support one after the other so as to increase the clogging of the support, without causing a deposit on the surface of the channels. Higher diameter particles are used first.
  • a first penetration according to the embodiment 2 is carried out.
  • the second particles used are titanium oxide particles having a mean particle diameter of 0.1 ⁇ m.
  • the powder is deflocculated via an adjuvant of the COATEX family.
  • the suspension contains no organic binder and the concentration of the powder is less than 20 g / l. The values of these two parameters are intended to obtain a very low viscosity.
  • the experimental conditions of the engobage carried out with this second suspension are defined in the table of the Fig. 14 . These conditions are identical to that of Example 2 to prevent the formation of a deposit.
  • three supports are made for each triplet Tr / Ta / Tv. These modified supports are calcined at 900 ° C. and then subjected to the same samplings and measurements as in the embodiment example 2 above.
  • the table of the fig.15 presents the flow rate values measured on these modified supports. In order to differentiate them from the previous example, the notation / 0,1 was added in the reference of each modified medium.
  • the high rate of emptying favors the homogeneity of flow rates.
  • the penetration of the thinnest powder could not be determined because it is not easy to distinguish particles of large particle size from smaller particle size, after sintering. However, no deposit was observed on the inner surface 4 of the support 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP03778408A 2002-10-25 2003-10-20 Membrane pour filtration tangentielle et son procede de fabrication Expired - Lifetime EP1562694B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0213359 2002-10-25
FR0213359A FR2846255B1 (fr) 2002-10-25 2002-10-25 Membrane pour filtration tangentielle et son procede de fabrication
PCT/FR2003/003097 WO2004039481A1 (fr) 2002-10-25 2003-10-20 Membrane pour filtration tangentielle et son procede de fabrication

Publications (2)

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EP1562694A1 EP1562694A1 (fr) 2005-08-17
EP1562694B1 true EP1562694B1 (fr) 2012-01-11

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US (1) US20060049094A1 (pt)
EP (1) EP1562694B1 (pt)
JP (1) JP4177813B2 (pt)
KR (1) KR101022931B1 (pt)
CN (1) CN100340328C (pt)
AT (1) ATE540748T1 (pt)
AU (1) AU2003285410B2 (pt)
BR (1) BR0315543B1 (pt)
CA (1) CA2503691C (pt)
DK (1) DK1562694T3 (pt)
ES (1) ES2380797T3 (pt)
FR (1) FR2846255B1 (pt)
HK (1) HK1083784A1 (pt)
NZ (1) NZ539521A (pt)
WO (1) WO2004039481A1 (pt)

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FR2869241B1 (fr) * 2004-04-23 2006-07-21 Tech Avancees & Membranes Ind Support a porosite modifiee et membrane pour la filtration tangentielle d'un fluide
FR2938199B1 (fr) * 2008-11-07 2011-11-25 Technlologies Avancees Et Membranes Ind Membrane de filtration, presentant une resistance a l'abrasion amelioree
FR2948295B1 (fr) * 2009-07-24 2012-07-13 Technologies Avancees & Membranes Ind Membrane de filtration, presentant une resistance a l'abrasion amelioree
FR2985595A1 (fr) 2012-01-10 2013-07-12 Alstom Technology Ltd Procede de filtration d'effluents gazeux nocifs d'une centrale nucleaire
FR2985438A1 (fr) * 2012-01-10 2013-07-12 Alstom Technology Ltd Membrane pour procede de filtration d'effluents gazeux d'une installation industrielle
FR2985437A1 (fr) 2012-01-10 2013-07-12 Alstom Technology Ltd Procede de filtration d'effluents gazeux d'une installation industrielle
FR3024665B1 (fr) * 2014-08-11 2020-05-08 Technologies Avancees Et Membranes Industrielles Element de separation par flux tangentiel integrant des obstacles a la circulation et procede de fabrication
CN107519764B (zh) * 2017-07-31 2021-02-02 成都易态科技有限公司 非对称管状过滤元件坯体的制造方法及其应用
CN107551826B (zh) * 2017-07-31 2023-11-14 成都易态科技有限公司 非对称管状过滤元件坯体的制造设备
CN107433137B (zh) * 2017-07-31 2020-12-01 成都易态科技有限公司 非对称管状过滤元件坯体的制造方法及其应用
SG11202005782UA (en) 2018-03-08 2020-09-29 Repligen Corp Tangential flow depth filtration systems and methods of filtration using same
NL2020923B1 (en) * 2018-05-14 2019-11-21 Stichting Wetsus European Centre Of Excellence For Sustainable Water Tech Method and filter system for microfiltering particles and/or droplets in a flow
WO2019227095A1 (en) 2018-05-25 2019-11-28 Repligen Corporation Tangential flow filtration systems and methods
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DK1562694T3 (da) 2012-05-07
JP2006503701A (ja) 2006-02-02
HK1083784A1 (en) 2006-07-14
ATE540748T1 (de) 2012-01-15
JP4177813B2 (ja) 2008-11-05
AU2003285410B2 (en) 2008-09-25
CA2503691C (fr) 2011-07-05
KR20050055039A (ko) 2005-06-10
CN1708348A (zh) 2005-12-14
WO2004039481A1 (fr) 2004-05-13
US20060049094A1 (en) 2006-03-09
KR101022931B1 (ko) 2011-03-16
BR0315543A (pt) 2005-08-23
BR0315543B1 (pt) 2011-11-01
ES2380797T3 (es) 2012-05-18
CN100340328C (zh) 2007-10-03
FR2846255A1 (fr) 2004-04-30
EP1562694A1 (fr) 2005-08-17
NZ539521A (en) 2006-10-27
FR2846255B1 (fr) 2005-01-28
AU2003285410A1 (en) 2004-05-25
CA2503691A1 (fr) 2004-05-13

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